Trimerization catalysts from sterically hindered salts

ABSTRACT

The present invention provides trimerization catalyst compositions having a sterically hindered carboxylate salt and methods to produce a polyisocyanurate/polyurethane foam using such trimerization catalyst compositions.

This Application is a Divisional application of application Ser. No.11/418,287, filed on 4 May 2006, now allowed.

BACKGROUND OF THE INVENTION

The present invention relates generally to catalyst systems,compositions comprising catalyst systems, polyisocyanurate/polyurethane(PIR/PUR) foam formulations, and methods of making PIR/PUR foams.

Typically, polyisocyanurate/polyurethane (PIR/PUR) foams are made byreacting a polyol and a polyisocyanate in the presence of a catalyst.Additional additives can be present. PIR/PUR foam products haveexcellent thermal stability and flame resistance. Isocyanurates retaintheir strength to temperatures of about 160° C. and are resistant tomost organic solvents, acids, alkali, ultraviolet light, and humidity.

Certain carboxylate salts, such as, for example, certain alkali metalcarboxylate salts, have been used as catalysts in the production ofPIR/PUR foams. The use of commercially available alkali metalcarboxylate salt catalysts, however, often leads to undesirable foamprocessing problems which are particularly significant in continuousfoam operations. A distinctive “step” is observed, which is normallyassociated with the onset of the trimerization process, when measuringthe rise speed profile of the foam, or by plotting the foam heightversus time. This trimerization “step” causes a significant change inthe speed of the foam rise; in essence, the foam expands at twodifferent rates during the foaming process. In a continuouspolyisocyanurate/polyurethane foam lamination operation, it is difficultto adjust the speed of the production unit to match the change in thespeed of the foam rise. The result can be foam overpacking or foam backflow. This undesirable rapid rise in foam height is particularlytroublesome when processing polyisocyanurate/polyurethane formulationsat a high Isocyanate Index. That is, the change in the rate of foam riseis much more dramatic at a higher Isocyanate Index. Consequently, it isa technical challenge to produce desirable low flammability foamproducts, with a high isocyanate index, when using conventional alkalimetal carboxylate salt catalysts.

As compared to alkali metal carboxylate salt catalysts, commerciallyavailable polyisocyanurate trimerization catalysts based onhydroxyalkylammonium carboxylate salts show different processability incontinuous operations. They provide a smoother rate of rise profile andhave a less significant trimerization “step.” That is, the rate of foamrise is more consistent, even at a higher Isocyanate Index. However,hydroxyalkylammonium carboxylate salt catalysts can be unstable attemperatures above about 100° C., decomposing into volatile amineby-products. This decomposition process causes the release of volatileamines and can impart an undesirable amine odor to finished foamproducts. The polymerization reactions that produce PIR/PUR foam arehighly exothermic, often leading to foam processing temperatures inexcess of 100° C. Hence, hydroxyalkylammonium carboxylate salt catalystscan provide more predictable foam processability, but sometimes at theexpense of a foam product with an undesirable amine odor.

Thus, there exists a need for a catalyst composition and a foamformulation that can offer a smooth rise profile—foam height versustime—for producing PIR/PUR foams in continuous operations. Further,there exists a need for a catalyst composition that performs well infoam formulations with a high Isocyanate Index. At the same time, suchcatalyst composition should provide equivalent or faster surface curewhen compared to commercially available catalyst systems, such that thefoam products made with the catalyst composition can have reducedsurface friability and enhanced surface adherence during the manufactureof finished products such as laminated foam panels. Optionally,depending upon the selection of the catalyst components, the catalystcomposition can be thermally stable at the temperatures which PIR/PURfoams normally encounter during manufacturing, and produce foams thatare substantially free of volatile amines and/or amine odors.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a novel catalyst composition forproducing a PIR/PUR foam comprising at least one sterically hinderedcarboxylate salt having the formula

wherein:

R¹, R², and R³ are selected independently from a C₁-C₁₈ alkyl, alkenyl,aryl, or aralkyl, any of which are substituted or unsubstituted;

n is an integer from 0 to 10, inclusive; and

M is an alkali metal ion or a quaternary ammonium ion.

In another aspect, the present invention discloses a compositioncomprising the contact product of at least one activehydrogen-containing compound, a catalyst composition comprising at leastone sterically hindered carboxylate salt, and at least one blowingagent, with the proviso that the at least one blowing agent is not achlorofluorocarbon (CFC). Further, the present invention also disclosesa composition comprising the contact product of at least onepolyisocyanate, a catalyst composition comprising at least onesterically hindered carboxylate salt, and at least one blowing agent,with the proviso that the at least one blowing agent is not achlorofluorocarbon (CFC). Due to the discovery that chlorofluorocarbons(CFCs) can deplete ozone in the stratosphere, this class of blowingagents is not desirable for use in the present invention.

The present invention also provides a method for preparingpolyisocyanurate/polyurethane (PIR/PUR) foam. This method comprisescontacting at least one polyisocyanate with at least one activehydrogen-containing compound, in the presence of at least one blowingagent, with the proviso that the at least one blowing agent is not aCFC, and an effective amount of a catalyst composition comprising atleast one sterically hindered carboxylate salt.

The catalyst composition of the present invention offers a substantiallyconsistent foam height rise versus time—even at a high IsocyanateIndex—and can provide an equivalent or faster surface cure during thepreparation of PIR/PUR foams. In another aspect of the presentinvention, the catalyst composition can be thermally stable at standardfoam processing temperatures, producing PIR/PUR foams which aresubstantially free of volatile amines and/or amine odors.

DEFINITIONS

The following definitions are provided in order to aid those skilled inthe art in understanding the detailed description of the presentinvention.

-   -   PIR—Polyisocyanurate.    -   PUR—Polyurethane.    -   Isocyanate Index—The actual amount of polyisocyanate used        divided by the theoretically required stoichiometric amount of        polyisocyanate required to react with all the active hydrogen in        the reaction mixture, multiplied by 100. Also known as (Eq        NCO/Eq of active hydrogen)×100.    -   pphp—parts by weight per hundred weight parts polyol.    -   DABCO® K15 catalyst from Air Products and Chemicals, Inc. (APCI)        is a 70% solution of an alkali metal carboxylate salt, potassium        2-ethylhexanoate (also known potassium octoate), in diethylene        glycol.    -   DABCO TMR® catalyst from APCI is a 75% solution of        2-hydroxypropyltrimethylammonium octoate in ethylene glycol    -   Polycat® 5 catalyst from APCI is a urethane catalyst, known        chemically as pentamethyldiethylenetriamine.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 presents a plot of the normalized foam height versus time forsterically hindered carboxylate salt catalyst 1, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about500.

FIG. 2 presents a plot of the rate of foam rise speed versus time forsterically hindered carboxylate salt catalyst 1, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about500.

FIG. 3 presents a plot of the normalized foam height versus time forsterically hindered carboxylate salt catalyst 2, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about500.

FIG. 4 presents a plot of the normalized foam height versus time forsterically hindered carboxylate salt catalysts 3 and 4, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about500.

FIG. 5 presents a plot of the normalized foam height versus time forsterically hindered carboxylate salt catalyst 5, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about270.

FIG. 6 presents a plot of the rate of foam rise speed versus time forsterically hindered carboxylate salt catalyst 5, the DABCO® K15catalyst, and the DABCO TMR® catalyst, at an Isocyanate Index of about270.

FIG. 7 presents a plot of the normalized foam height versus time forinventive catalyst combinations of the DABCO® K15 catalyst andsterically hindered carboxylate salt catalyst 1, at an Isocyanate Indexof about 250.

FIG. 8 presents a plot of the rate of foam rise speed versus time forinventive catalyst combinations of the DABCO® K15 catalyst andsterically hindered carboxylate salt catalyst 1, at an Isocyanate Indexof about 250.

FIG. 9 presents a plot of the foam height versus time for foamformulations using trichlorofluoromethane and n-pentane blowing agents.

FIG. 10 presents a plot of the rate of foam rise speed versus time forfoam formulations using trichlorofluoromethane and n-pentane blowingagents.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a novel catalyst compositioncomprising at least one sterically hindered carboxylate salt. This novelcatalyst system can be used as a polyisocyanate trimerization catalystsystem for producing polyisocyanurate/polyurethane (PIR/PUR) foams.Further, the present invention also is directed to novel compositionscomprising the contact product of at least one activehydrogen-containing compound, at least one blowing agent, and a catalystcomposition comprising at least one sterically hindered carboxylatesalt. Additionally, the present invention is directed to novelcompositions comprising the contact product of at least onepolyisocyanate, at least one blowing agent, and a catalyst compositioncomprising at least one sterically hindered carboxylate salt. Thesenovel compositions can be used together with additional components toproduce PIR/PUR foams.

Also, the present invention provides a method for preparing a PIR/PURfoam which comprises contacting at least one polyisocyanate with atleast one active hydrogen-containing compound in the presence of atleast one blowing agent and an effective amount of a catalystcomposition comprising at least one sterically hindered carboxylatesalt. Additionally, rigid PIR/PUR foams can be produced with the novelcatalyst system and novel compositions of the present invention byseveral methods known within the art.

A catalyst composition comprising at least one sterically hinderedcarboxylate salt can be used to trimerize isocyanates to produceisocyanurates. Generally, any amount of the at least one stericallyhindered carboxylate salt can be used in the compositions of the presentinvention. As used in practice, catalyst systems for PIR/PUR foamstypically include solutions of carboxylate salts in, for example, adiluent such as ethylene glycol. When a quantity by weight of thecatalyst composition of the present invention is discussed, the quantitywill exclude the effect of the diluent, unless stated otherwise. As anexample, if 10 grams of a 50% solution of potassium pivalate catalyst inethylene glycol were used in a given application, the amount of thepotassium pivalate salt catalyst would equal 5 grams. Hence, 5 grams ofthat catalyst component would be used in calculating any weight ratiosof that component in relation to, for example, the amount of activehydrogen-containing compound or the amount of polyol.

Applicants disclose several types of ranges in the present invention.These include, but are not limited to, a range of temperatures; a rangeof number of atoms; a range of foam density; a range of IsocyanateIndex; and a range of pphp for the blowing agent, water, surfactant,flame retardant, urethane catalyst, and catalyst composition comprisingat least one sterically hindered carboxylate salt. When Applicantsdisclose or claim a range of any type, Applicants' intent is to discloseor claim individually each possible number that such a range couldreasonably encompass, as well as any sub-ranges and combinations ofsub-ranges encompassed therein. For example, when the Applicantsdisclose or claim a chemical moiety having a certain number of carbonatoms, Applicants' intent is to disclose or claim individually everypossible number that such a range could encompass, consistent with thedisclosure herein. For example, the disclosure that “R¹” can be an alkylgroup having up to 18 carbon atoms, or in alternative language a C₁ toC₁₈ alkyl group, as used herein, refers to a “R¹” group that can beselected independently from an alkyl group having 1, 2, 3, 4, 5, 6, 7,8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as well as anyrange between these two numbers (for example, a C₁ to C₈ alkyl group),and also including any combination of ranges between these two numbers(for example, a C₃ to C₅ and C₇ to C₁₀ alkyl group). Likewise, thisapplies to all other carbon ranges disclosed herein, for example, C₁ toC₁₈ ranges for R² and R³; alkoxy groups having up to 10 carbon atoms;etc.

Similarly, another representative example follows for the parts byweight of the catalyst composition comprising at least one stericallyhindered carboxylate salt per hundred weight parts of the at least oneactive hydrogen-containing compound in a composition or a foamformulation. If the at least one active hydrogen-containing compound isan at least one polyol, the parts by weight per hundred weight partspolyol is abbreviated as pphp. Hence, by the disclosure that thecatalyst composition comprising at least one sterically hinderedcarboxylate salt is present in an amount from about 0.05 to about 10pphp, for example, Applicants intend to recite that the pphp can beselected from about 0.05, about 0.06, about 0.07, about 0.08, about0.09, about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about 0.6,about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about 4,about 5, about 6, about 7, about 8, about 9, or about 10. Likewise, allother ranges disclosed herein should be interpreted in a manner similarto these two examples.

Applicants reserve the right to proviso out or exclude any individualmembers of any such group, including any sub-ranges or combinations ofsub-ranges within the group, that can be claimed according to a range orin any similar manner, if for any reason Applicants choose to claim lessthan the full measure of the disclosure, for example, to account for areference that Applicants may be unaware of at the time of the filing ofthe application. Further, Applicants reserve the right to proviso out orexclude any individual substituents, analogs, compounds, ligands,structures, or groups thereof, or any members of a claimed group, if forany reason Applicants choose to claim less than the full measure of thedisclosure, for example, to account for a reference that Applicants maybe unaware of at the time of the filing of the application.

Although not required, another aspect of the present invention providesa thermally stable catalyst system. When used to describe this feature,a compound is defined as thermally stable at a given temperature when itdoes not decompose or release volatile amines and/or related amine odorsat the given temperature. A hydroxyalkylammonium salt catalyst, such asthe DABCO TMR® catalyst, can become unstable when the PIR/PUR foamtemperature reaches above about 100° C. during foam processing. At theseelevated temperatures, due to the nature of the quaternary amine salt,the DABCO TMR® catalyst can release volatile amine components. Catalystcompositions of the present invention which are based on quaternaryammonium salts are thermally stable if they do not have eitherfunctional groups (e.g., hydroxyl) or hydrogen on the carbon atom at theβ-position relative to the quaternary nitrogen.

Thus, sterically hindered carboxylate salts with alkali metal ions, forexample, lithium, sodium, potassium, and rubidium, are thermally stablecatalyst compositions within the scope of the present invention.Quaternary ammonium salts with thermal stability include, but are notlimited to, tetramethylammonium pivalate, tetraethylammonium pivalate,tetrapropylammonium pivalate, tetrabutylammonium pivalate,tetramethylammonium triethylacetate, tetraethylammonium triethylacetate,tetrapropylammonium triethylacetate, tetrabutylammonium triethylacetate,tetramethylammonium neoheptanoate, tetraethylammonium neoheptanoate,tetrapropylammonium neoheptanoate, tetrabutylammonium neoheptanoate,tetramethylammonium neooctanoate, tetraethylammonium neooctanoate,tetrapropylammonium neooctanoate, tetrabutylammonium neooctanoate,tetramethylammonium neodecanoate, tetraethylammonium neodecanoate,tetrapropylammonium neodecanoate, tetrabutylammonium neodecanoate, andthe like. Such salts can be employed individually or in any combinationthereof.

In one aspect of the present invention, the catalyst compositioncomprising at least one sterically hindered carboxylate salt has thermalstability up to about 150° C., wherein no or substantially no volatileamine compounds are emitted. Typical foam temperatures resulting fromthe exothermic reactions during the processing of PIR/PUR foam can be inthe range of about 80° C. to about 150° C. In a further aspect, thecatalyst system of the present invention has thermal stability up toabout 175° C., about 200° C., about 220° C., about 240° C., or about250° C.

The sterically hindered carboxylate salts of the catalyst composition ofthe present invention can be produced, for example, by the reaction ofan organic acid with an alkali hydroxide. In another aspect of thepresent invention, the sterically hindered carboxylate salt can beproduced by the reaction of an organic acid with a tetraalkylammoniumhydroxide, or a reaction of an organic acid with a tertiary aminefollowed by a reaction with an epoxy compound. The latter reaction withan epoxy can lead to a hydroxyalkyl quaternary compound (for example,2-hydroxypropyltrimethyl-ammonium) which is unstable at elevatedtemperatures. However, such reaction products can be employed in thepresent invention.

Although not a requirement of the present invention, the catalyst systemor novel compositions of the present invention can further compriseother catalytic materials or carboxylate salts in any amount. These caninclude, but are not limited to, alkali metal α,β-unsaturatedcarboxylate salts, alkaline earth metal α,β-unsaturated carboxylatesalts, quaternary ammonium α,β-unsaturated carboxylate salts, alkalimetal carboxylate salts, alkaline earth metal carboxylate salts,quaternary ammonium carboxylate salts, or any combination thereof.Illustrative examples of α,β-unsaturated carboxylate salts include, butare not limited to, potassium acrylate, tetramethylammonium acrylate,tetraethylammonium acrylate, tetrapropylammonium acrylate,tetrabutylammonium acrylate, potassium methacrylate, tetramethylammoniummethacrylate, tetraethylammonium methacrylate, tetrapropylammoniummethacrylate, tetrabutylammonium methacrylate, mono-potassium fumarate,bis-potassium fumarate, mono-tetramethylammonium fumarate,bis-tetramethylammonium fumarate, potassium tetramethylammoniumfumarate, mono-tetraethylammonium fumarate, bis-tetraethylammoniumfumarate, potassium tetraethylammonium fumarate,mono-tetrapropylammonium fumarate, bis-tetrapropylammonium fumarate,potassium tetrapropylammonium fumarate, mono-tetrabutylammoniumfumarate, bis-tetrabutylammonium fumarate, potassium tetrabutylammoniumfumarate, mono-potassium maleate, bis-potassium maleate,mono-tetramethylammonium maleate, bis-tetramethylammonium maleate,potassium tetramethylammonium maleate, mono-tetraethylammonium maleate,bis-tetraethylammonium maleate, potassium tetraethylammonium maleate,mono-tetrapropylammonium maleate, bis-tetrapropylammonium maleate,potassium tetrapropylammonium maleate, mono-tetrabutylammonium maleate,bis-tetrabutylammonium maleate, potassium tetrabutylammonium maleate,trimethyl(2-hydroxyethyl)ammonium acrylate,triethyl(2-hydroxyethyl)ammonium acrylate,tripropyl(2-hydroxyethyl)ammonium acrylate,tributyl(2-hydroxyethyl)ammonium acrylate,dimethylbenzyl(2-hydroxypropyl)ammonium acrylate,dimethylbenzyl(2-hydroxyethyl)ammonium acrylate,trimethyl(2-hydroxyethyl)ammonium methacrylate,triethyl(2-hydroxyethyl)ammonium methacrylate,tripropyl(2-hydroxyethyl)ammonium methacrylate,tributyl(2-hydroxyethyl)ammonium methacrylate,dimethylbenzyl(2-hydroxypropyl)ammonium methacrylate,dimethylbenzyl(2-hydroxyethyl)ammonium methacrylate,bis-(trimethyl(2-hydroxyethyl)ammonium) maleate,bis-(triethyl(2-hydroxyethyl)ammonium)maleate,bis-(tripropyl(2-hydroxyethyl)ammonium)maleate,bis-(tributyl(2-hydroxyethyl)ammonium)maleate,bis-(dimethylbenzyl(2-hydroxypropyl)ammonium)maleate,bis-(dimethylbenzyl(2-hydroxyethyl)ammonium)maleate,bis-(trimethyl(2-hydroxyethyl)ammonium)fumarate,bis-(triethyl(2-hydroxyethyl)ammonium)fumarate,bis-(tripropyl(2-hydroxyethyl)ammonium)fumarate,bis-(tributyl(2-hydroxyethyl)ammonium)fumarate,bis-(dimethylbenzyl(2-hydroxypropyl)ammonium)fumarate,bis-(dimethylbenzyl(2-hydroxyethyl)ammonium)fumarate, and the like, orany combination thereof.

Illustrative examples of alkali metal, alkaline earth metal, andquaternary ammonium carboxylate salts include, but are not limited to,potassium formate, potassium acetate, potassium propionate, potassiumbutanoate, potassium pentanoate, potassium hexanoate, potassiumheptanoate, potassium octoate, potassium 2-ethylhexanoate, potassiumdecanoate, potassium butyrate, potassium isobutyrate, potassium nonante,potassium stearate, sodium octoate, lithium stearate, sodium caprioate,lithium octoate, 2-hydroxypropyltrimethylammonium octoate solution, andthe like, or any combination thereof.

It is also within the scope of the catalyst composition of thisinvention to include mixtures or combinations of more that onesterically hindered carboxylate salt. Additionally, the catalyst systemor the novel compositions of the present invention can also furthercomprise at least one urethane catalyst.

The term “contact product” is used herein to describe compositionswherein the components are contacted together in any order, in anymanner, and for any length of time. For example, the components can becontacted by blending or mixing. Further, contacting of any componentcan occur in the presence or absence of any other component of thecompositions or foam formulations described herein. Combining additionalcatalyst components can be done by any method known to one of skill inthe art. For example, in one aspect of the present invention, catalystcompositions can be prepared by combining or contacting the at least onesterically hindered carboxylate salt with an optional alkali metalcarboxylate salt. This typically occurs in solution form. In anotheraspect, the catalyst composition can be prepared by first mixing therespective carboxylic acids, followed by neutralization to form thecorresponding salts.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

Sterically Hindered Carboxylate Salts

Catalyst compositions of the present invention comprise at least onesterically hindered carboxylate salt. The at least one stericallyhindered carboxylate salt is particularly useful for producing PIR/PURfoams. Further, catalyst compositions within the scope of the presentinvention can comprise at least one sterically hindered carboxylate salthaving the formula

wherein:

R¹, R², and R³ are selected independently from a C₁-C₁₈ alkyl, alkenyl,aryl, or aralkyl, any of which are substituted or unsubstituted;

n is an integer from 0 to 10, inclusive; and

M is an alkali metal ion or a quaternary ammonium ion.

Unless otherwise specified, alkyl and alkenyl groups described hereinare intended to include all structural isomers, linear or branched, of agiven structure; for example, all enantiomers and all diasteriomers areincluded within this definition. As an example, unless otherwisespecified, the term propyl is meant to include n-propyl and iso-propyl,while the term butyl is meant to include n-butyl, iso-butyl, t-butyl,sec-butyl, and so forth. Similarly, substituted alkyl, alkenyl, aryl,and aralkyl groups described herein are intended to include substitutedanalogs of a given structure. For example, the substituents on alkyl,alkenyl, aryl, and aralkyl groups can include, but are not limited to,halides; hydroxyl groups; amino groups; alkoxy, alkylamino, ordialkylamino groups having up to 10 carbon atoms; or combinationsthereof.

Non-limiting examples of alkyl groups which can be present in the atleast one sterically hindered carboxylate salt include, but are notlimited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl,nonyl, or decyl, and the like. Examples of alkenyl groups within thescope of the present invention include, but are not limited to, ethenyl,propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl,decenyl, and the like. Aryl and aralkyl (aralkyl is defined as anaryl-substituted alkyl or arylalkyl) groups include phenyl,alkyl-substituted phenyl, naphthyl, alkyl-substituted naphthyl, and thelike. For example, non-limiting examples of aryl and aralkyl groupsuseful in the present invention include, but are not limited to, phenyl,tolyl, benzyl, dimethylphenyl, trimethylphenyl, phenylethyl,phenylpropyl, phenylbutyl, propyl-2-phenylethyl, and the like.

In one aspect of the present invention, R¹, R², and R³ are selectedindependently from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,octyl, phenyl, tolyl, and benzyl. In another aspect, R¹, R², and R³ areselected independently from methyl, ethyl, propyl, and butyl. Inaccordance with a further aspect of the present invention, R¹, R², andR³ of the sterically hindered structure are not hydrogen atoms.

In another aspect, M is an ion of lithium, potassium, sodium, orrubidium. In yet another aspect, M is a potassium ion. Quaternaryammonium ions useful in the present invention include, but are notlimited to, tetramethylammonium, tetraethylammonium,tetrapropylammonium, tetrabutylammonium, dimethyldiallylammonium,trimethyl(2-hydroxypropyl)ammonium, triethyl(2-hydroxypropyl)ammonium,tripropyl(2-hydroxypropyl)ammonium, tributyl(2-hydroxypropyl)ammonium,trimethyl(2-hydroxyethyl)ammonium, triethyl(2-hydroxyethyl)ammonium,tripropyl(2-hydroxyethyl)ammonium, tributyl(2-hydroxyethyl)ammonium,dimethylbenzyl(2-hydroxypropyl)ammonium,dimethylbenzyl(2-hydroxyethyl)ammonium, and the like, or any combinationthereof. In a further aspect of the present invention, M is atetramethylammonium ion or a dimethyldiallylammonium ion.

The integer n in the above formula can range from 0 to 10, inclusive, inone aspect of the present invention. In another aspect, n can range from0 to 5, inclusive. In still another aspect, n equals zero. As anexample, when R¹, R², and R³ are each a methyl group, M is a potassiumion, and n equals zero, the sterically hindered carboxylate salt ispotassium pivalate.

In another aspect of the present invention, the at least one stericallyhindered carboxylate salt is an alkali metal carboxylate salt or aquaternary ammonium carboxylate salt, or a combination thereof. In yetanother aspect, the sterically hindered carboxylate salts and acidswithin the scope of this invention comprise at least one quaternarycarbon moiety. That is, as a minimum, one carbon atom within thecarboxylate salt or carboxylic acid structures and materials describedherein is a quaternary carbon. As used herein, a quaternary carbon isdefined as a carbon that is bonded to four other carbon atoms. Thisquaternary carbon moiety can be further illustrated, for example, by thecarboxylate salt and acid species that follow.

Suitable sterically hindered carboxylate salts of the present inventioninclude, but are not limited to, potassium pivalate, tetramethylammoniumpivalate, 2-hydroxylpropyltrimethylammonium pivalate,2-hydroxylpropyltriethylammonium pivalate, tetraethylammonium pivalate,tetrapropylammonium pivalate, tetrabutylammonium pivalate,dimethyldiallylammonium pivalate, potassium triethylacetate,tetramethylammonium triethylacetate, 2-hydroxylpropyltrimethylammoniumtriethylacetate, 2-hydroxylpropyltriethylammonium triethylacetate,tetraethylammonium triethylacetate, tetrapropylammonium triethylacetate,tetrabutylammonium triethylacetate, potassium neoheptanoate,tetramethylammonium neoheptanoate, 2-hydroxylpropyltrimethyl-ammoniumneoheptanoate, 2-hydroxylpropyltriethylammonium neoheptanoate,tetraethylammonium neoheptanoate, tetrapropylammonium neoheptanoate,tetrabutyl-ammonium neoheptanoate, potassium neooctanoate,tetramethylammonium neooctanoate, 2-hydroxylpropyltrimethylammoniumneooctanoate, 2-hydroxylpropyltriethylammonium neooctanoate,tetraethylammonium neooctanoate, tetrapropyl-ammonium neooctanoate,tetrabutylammonium neooctanoate, potassium neodecanoate,tetramethylammonium neodecanoate, 2-hydroxylpropyltrimethylammoniumneodecanoate, 2-hydroxylpropyltriethylammonium neodecanoate,tetraethylammonium neodecanoate, tetrapropylammonium neodecanoate,tetrabutylammonium neodecanoate, and the like, or any combinationthereof.

In another aspect of the present invention, the at least one stericallyhindered carboxylate salt is a tetraalkylammonium carboxylate salt. Inyet another aspect, the at least one sterically hindered carboxylate istetramethylammonium pivalate, dimethyldiallylammonium pivalate,potassium pivalate, potassium neoheptanoate, potassium neodecanoate, ora combination thereof. In still another aspect, the at least onesterically hindered carboxylate salt is potassium pivalate.

In a further aspect, the at least one sterically hindered carboxylatesalt is a salt of a carboxylic acid, for example, an alkali metal saltor quaternary ammonium salt of a sterically hindered carboxylic acid.Suitable carboxylic acids within the scope of the present inventioninclude, but are not limited to, pivalic, triethylacetic, neohexanoic,neoheptanoic, neooctanoic, neodecanoic, neoundecanoic, neododecanoic,and the like, mixtures thereof, or any combination thereof.

Polyisocyanates

Polyisocyanates that are useful in the PIR/PUR foam formation processinclude, but are not limited to, hexamethylene diisocyanate, isophoronediisocyanate, phenylene diisocyante, toluene diisocyanate (TDI),diphenyl methane diisocyanate isomers (MDI), hydrated MDI and1,5-naphthalene diisocyanate. For example, 2,4-TDI, 2,6-TDI, andmixtures thereof, can be readily employed in the present invention.Other suitable mixtures of diisocyanates include, but are not limitedto, those known in the art as crude MDI, or PAPI, which contain4,4′-diphenylmethane diisocyanate along with other isomeric andanalogous higher polyisocyanates. In another aspect of this invention,prepolymers of polyisocyanates comprising a partially pre-reactedmixture of polyisocyanates and polyether or polyester polyol aresuitable. In still another aspect, the polyisocyanate comprises MDI, orconsists essentially of MDI or mixtures of MDI's.

The catalyst system, compositions, and methods of producing PIR/PUR foamof the present invention can be used to manufacture many types of foam.This catalyst system is useful, for example, in the formation of foamproducts for rigid and flame retardant applications, which usuallyrequire a high Isocyanate Index. As defined previously, Isocyanate Indexis the actual amount of polyisocyanate used divided by the theoreticallyrequired stoichiometric amount of polyisocyanate required to react withall the active hydrogen in the reaction mixture, multiplied by 100. Forpurposes of the present invention, Isocyanate Index is represented bythe equation: Isocyanate Index=(Eq NCO/Eq of active hydrogen)×100,wherein Eq NCO is the number of NCO functional groups in thepolyisocyanate, and Eq of active hydrogen is the number of equivalentactive hydrogen atoms.

Foam products which are produced with an Isocyanate Index from about 80to about 800 are within the scope of this invention. In accordance withother aspects of the present invention, the Isocyanate Index ranges fromabout 100 to about 700, from about 150 to about 650, from about 200 toabout 600, or from about 250 to about 500.

Polyols

Active hydrogen-containing compounds for use with the foregoingpolyisocyanates in forming the polyisocyanurate/polyurethane foams ofthis invention can be any of those organic compounds having at least twohydroxyl groups such as, for example, polyols. Polyols that aretypically used in PIR/PUR foam formation processes include polyalkyleneether and polyester polyols. The polyalkylene ether polyol includes thepoly(alkyleneoxide) polymers such as poly(ethyleneoxide) andpoly(propyleneoxide) polymers and copolymers with terminal hydroxylgroups derived from polyhydric compounds, including diols and triols,These include, but are not limited to, ethylene glycol, propyleneglycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentylglycol, diethylene glycol, dipropylene glycol, pentaerythritol,glycerol, diglycerol, trimethylol propane, cyclohexane diol, and sugarssuch as sucrose and like low molecular weight polyols.

Amine polyether polyols can be used in the present invention. These canbe prepared when an amine such as, for example, ethylenediamine,diethylenetriamine, tolylenediamine, diphenylmethanediamine, ortriethanolamine is reacted with ethylene oxide or propylene oxide.

In another aspect of the present invention, a single high molecularweight polyether polyol, or a mixture of high molecular weight polyetherpolyols, such as mixtures of different multifunctional materials and/ordifferent molecular weight or different chemical composition materialscan be used.

In yet another aspect of the present invention, polyester polyols can beused, including those produced when a dicarboxylic acid is reacted withan excess of a diol. Non-limiting examples include adipic acid orphathalic acid or phthalic anhydride reacting with ethylene glycol orbutanediol. Polyols useful in the present invention can be produced byreacting a lactone with an excess of a diol, for example, caprolactonereacted with propylene glycol. In a further aspect, activehydrogen-containing compounds such as polyester polyols and polyetherpolyols, and combinations thereof, are useful in the present invention.

Blowing Agents

In accordance with the compositions, foam formulations, and methods ofproducing PIR/PUR foam within the scope of the present invention,suitable blowing agents that can be used alone or in combinationinclude, but are not limited to, water, methylene chloride, acetone,hydrofluorocarbons (HFCs), hydrochlorofluorocarbons (HCFCs), andhydrocarbons. Examples of HFCs include, but are not limited to,HFC-245fa, HFC-134a, and HFC-365; illustrative examples of HCFCsinclude, but are not limited to, HCFC-141b, HCFC-22, and HCFC-123.Exemplary hydrocarbons include, but are not limited to, n-pentane,iso-pentane, cyclopentane, and the like, or any combination thereof. Inone aspect of the present invention, the blowing agent or mixture ofblowing agents comprises at least one hydrocarbon. In another aspect,the blowing agent comprises n-pentane. Yet, in another aspect of thepresent invention, the blowing agent consists essentially of n-pentaneor mixtures of n-pentane with one or more blowing agents.

Due to the discovery that chlorofluorocarbons (CFCs) can deplete ozonein the stratosphere, this class of blowing agents is not desirable foruse in the present invention. A chlorofluorocarbon (CFC) is an alkane inwhich all hydrogen atoms are substituted with chlorine and fluorineatoms. Examples of CFCs include trichlorofluoromethane anddichlorodifluoromethane. Thus, compositions in accordance with thepresent invention comprise only non-CFC blowing agents.

The amount of blowing agent used can vary based on, for example, theintended use and application of the foam product and the desired foamstiffness and density. In the compositions, foam formulations andmethods for preparing a polyisocyanurate/polyurethane foam of thepresent invention, the blowing agent is present in amounts from about 10to about 80 parts by weight per hundred weight parts of the at least oneactive hydrogen-containing compound. In another aspect, the blowingagent is present in amounts from about 12 to about 60, from about 14 toabout 50, or from about 16 to about 40, parts by weight per hundredweight parts of the at least one active hydrogen-containing compound. Ifthe at least one active hydrogen-containing compound is an at least onepolyol, the blowing agent is present in amounts from about 10 to about80 parts by weight per hundred weight parts polyol (pphp), from about 12to about 60 pphp, from about 14 to about 50 pphp, or from about 16 toabout 40 pphp.

If water is present in the formulation, for use as a blowing agent orotherwise, water is present in amounts up to about 15 parts by weightper hundred weight parts of the at least one active hydrogen-containingcompound. Likewise, if the at least one active hydrogen-containingcompound is an at least one polyol, water can range from 0 to about 15pphp. In another aspect, water can range from 0 to about 10 pphp, from 0to about 8 pphp, from 0 to about 6 pphp, or from 0 to about 4 pphp.

Urethane Catalyst

Urethane catalysts accelerate the reaction to form polyurethanes, andcan be used as a further component of the catalyst systems andcompositions of the present invention to producepolyisocyanurate/polyurethane foam. Urethane catalysts suitable for useherein include, but are not limited to, metal salt catalysts, such asorganotins, and amine compounds, such as triethylenediamine (TEDA),N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine(commercially available as the DABCO® NMM catalyst), N-ethylmorpholine(commercially available as the DABCO® NEM catalyst), triethylamine(commercially available as the DABCO® TETN catalyst),N,N′-dimethylpiperazine,1,3,5-tris(dimethylaminopropyl)hexahydrotriazine (commercially availableas the Polycat® 41 catalyst), 2,4,6-tris(dimethylaminomethyl)phenol(commercially available as the DABCO TMR® 30 catalyst),N-methyldicyclohexylamine (commercially available as the Polycat® 12catalyst), pentamethyldipropylene triamine (commercially available asthe Polycat® 77 catalyst),N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine,pentamethyldiethylenetriamine (commercially available as the Polycat® 5catalyst), hexamethyltriethylenetetramine,heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine(commercially available as the Polycat® 8 catalyst),pentamethyldipropylenetriamine, triethanolamine, dimethylethanolamine,bis(dimethylaminoethyl)ether (commercially available as the DABCO® BL19catalyst), tris(3-dimethylamino)propylamine (commercially available asthe Polycat® 9 catalyst), 1,8-diazabicyclo[5.4.0]undecene (commerciallyavailable as the DABCO® DBU catalyst) or its acid blocked derivatives,and the like, as well as any mixture thereof. Particularly useful as aurethane catalyst for foam applications related to the present inventionis the Polycat® 5 catalyst, which is known chemically aspentamethyldiethylenetriamine.

For preparing a polyisocyanurate/polyurethane foam of the presentinvention, the urethane catalyst can be present in the formulation from0 to about 10 pphp, from 0 to about 8 pphp, from 0 to about 6 pphp, from0 to about 4 pphp, from 0 to about 2 pphp, or from 0 to about 1 pphp. Inanother aspect, the urethane catalyst is present from 0 to about 0.8pphp, from 0 to about 0.6 pphp, from 0 to about 0.4 pphp, or from 0 toabout 0.2 pphp.

Miscellaneous Additives

Depending upon on the requirements during foam manufacturing or for theend-use application of the foam product, various additives can beemployed in the PIR/PUR foam formulation to tailor specific properties.These include, but are not limited to, cell stabilizers, flameretardants, chain extenders, epoxy resins, acrylic resins, fillers,pigments, or any combination thereof. It is understood that othermixtures or materials that are known in the art can be included in thefoam formulations and are within the scope of the present invention.

Cell stabilizers include surfactants such as organopolysiloxanes.Silicon surfactants can be present in the foam formulation in amountsfrom about 0.5 to about 10 pphp, about 0.6 to about 9 pphp, about 0.7 toabout 8 pphp, about 0.8 to about 7 pphp, about 0.9 to about 6 pphp,about 1 to about 5 pphp, or about 1.1 to about 4 pphp. Useful flameretardants include halogenated organophosphorous compounds andnon-halogenated compounds. A non-limiting example of a halogenated flameretardant is trichloropropylphosphate (TCPP). For example,triethylphosphate ester (TEP) and DMMP are non-halogenated flameretardants. Depending on the end-use foam application, flame retardantscan be present in the foam formulation in amounts from 0 to about 50pphp, from 0 to about 40 pphp, from 0 to about 30 pphp, or from 0 toabout 20 pphp. In another aspect, the flame retardant is present from 0to about 15 pphp, 0 to about 10 pphp, 0 to about 7 pphp, or 0 to about 5pphp. Chain extenders such as ethylene glycol and butane diol can alsobe employed in the present invention. Ethylene glycol, for instance, canalso be present in the formulation as a diluent or solvent for thecarboxylate salt catalysts of the present invention.

Polyisocyanurate/Polyurethane Foam Formulation and Process

One aspect of the present invention provides for a compositioncomprising the contact product of at least one activehydrogen-containing compound, at least one blowing agent, and a catalystcomposition comprising at least one sterically hindered carboxylatesalt. Another aspect provides a composition comprising the contactproduct of at least one polyisocyanate, at least one blowing agent, anda catalyst composition comprising at least one sterically hinderedcarboxylate salt. In both of these two compositions, the composition canfurther comprise at least one urethane catalyst. Likewise, thecompositions can further comprise at least one additive selected from atleast one cell stabilizer, at least one flame retardant, at least onechain extender, at least one epoxy resin, at least one acrylic resin, atleast one filler, at least one pigment, or any combination thereof.

The present invention provides a method for preparing apolyisocyanurate/polyurethane (PIR/PUR) foam which comprises contactingat least one polyisocyanate with at least one active hydrogen-containingcompound, in the presence of at least one blowing agent and an effectiveamount of a catalyst composition comprising at least one stericallyhindered carboxylate salt. In accordance with the method of the presentinvention, PIR/PUR foams can be produced having a density from about 20Kg/m³ to about 250 Kg/m³ (about 1.25 lb/ft³ to about 15.5 lb/ft³), orfrom about 24 Kg/m³ to about 60 Kg/m³ (about 1.5 lb/ft³ to about 3.75lb/ft³).

In another aspect, the method of the present invention offers asubstantially consistent foam height rise versus time—even at a highIsocyanate Index—that is highly desired for continuous foammanufacturing operations. The method for preparing PIR/PUR foams alsocan provide equivalent or faster surface cure when compared to othercommercially available catalyst systems, such that the PIR/PUR foam hasenhanced surface adherence, useful for the production are articles suchas laminated foam panels.

Optionally, in yet another aspect, the method of the present inventioncan produce PIR/PUR foams with no or substantially no undesirable amineodor. Dependent upon the selection of the specific at least onesterically hindered carboxylate salt, this method can provide thermalstability at the temperatures which PIR/PUR foams normally encounterduring manufacturing, even those foams formulated with a high IsocyanateIndex. In a further aspect, the method for preparing PIR/PUR foam hasthermally stability up to about 150° C., or about 175° C., or about 200°C., or about 220° C., or about 240° C., or about 250° C. In a stillfurther aspect, the method of the present invention produces PIR/PURfoam that is substantially free of volatile amines and/or amine odors.

The catalyst composition comprising at least one sterically hinderedcarboxylate salt should be present in the foam formulation in acatalytically effective amount. In PIR/PUR foam formulations of thepresent invention, the catalyst composition is present in amounts fromabout 0.05 to about 10 parts by weight per hundred weight parts of theat least one active hydrogen-containing compound, excluding the weightcontribution of the catalyst system diluent. In another aspect, thecatalyst composition is present in amounts from about 0.4 to about 9parts, or from about 0.8 to about 8 parts, by weight per hundred weightparts of the at least one active hydrogen-containing compound. If the atleast one active hydrogen-containing compound is an at least one polyol,the catalyst composition is present in amounts from about 0.05 to about10 parts by weight per hundred weight parts polyol (pphp). In anotheraspect, the catalyst composition is present in amounts from about 0.2 toabout 9.5 pphp, about 0.4 to about 9 pphp, about 0.6 to about 8.5 pphp,or about 0.8 to about 8 pphp.

In accordance with one aspect of the method of the present invention,the components of the foam formulation are contacted substantiallycontemporaneously. For example, at least one polyisocyanate, at leastone active hydrogen-containing compound, at least one blowing agent andan effective amount of a catalyst composition comprising at least onesterically hindered carboxylate salt, are contacted together. Given thenumber of components involved in PIR/PUR formulations, there are manydifferent orders of combining the components, and one of skill in theart would realize that varying the order of addition of the componentsfalls within the scope of the present invention. As well, for each ofthe different orders of combining the aforementioned components of thefoam formulation, the foam formulation of the present invention canfurther comprise at least one urethane catalyst. In addition, the methodof producing PIR/PUR foams can further comprise the presence of at leastone additive selected from at least one cell stabilizer, at least oneflame retardant, at least one chain extender, at least one epoxy resin,at least one acrylic resin, at least one filler, at least one pigment,or any combination thereof. In one aspect of the present invention, allof the components, including optional components, are contactedsubstantially contemporaneously.

In another aspect of the present invention, a premix of ingredientsother than the at least one polyisocyanate are contacted first, followedby the addition of the at least one polyisocyanate. For example, the atleast one active hydrogen-containing compound, the at least one blowingagent, and the catalyst composition of the present invention arecontacted initially to form a premix. The premix is then contacted withthe at least one polyisocyanate to produce PIR/PUR foams in accordancewith the method of the present invention. In a further aspect of thepresent invention, the same method can be employed, wherein the premixfurther comprises at least one urethane catalyst. Likewise, the premixcan further comprise at least one additive selected from at least onecell stabilizer, at least one flame retardant, at least one chainextender, at least one epoxy resin, at least one acrylic resin, at leastone filler, at least one pigment, or any combination thereof.

One aspect of the present invention provides a method for preparing apolyisocyanurate/polyurethane foam comprising (a) forming a premixcomprising:

-   -   i) at least one polyol;    -   ii) about 10 to about 80 parts by weight per hundred weight        parts of the polyol (pphp) blowing agent;    -   iii) about 0.5 to about 10 pphp silicon surfactant;    -   iv) zero to about 10 pphp water;    -   v) zero to about 50 pphp flame retardant;    -   vi) zero to about 10 pphp urethane catalyst; and    -   vii) about 0.05 to about 10 pphp of a catalyst composition        comprising at least one sterically hindered carboxylate salt;        and        (b) contacting the premix with at least one polyisocyanate at an        Isocyanate Index from about 80 to about 800.

As indicated previously, the blowing agent is not a chlorofluorocarbon(CFC).

EXAMPLES

The foams of examples 1-7 were produced by adding a catalyst of thepresent invention into a premix of a polyol, flame retardant (TCPP),surfactant, urethane catalyst (Polycat® 5 catalyst), and blowing agent(n-pentane), in a 32-oz (951 ml) metal cup. This composition was mixedfor about 10 seconds (s) at about 6,000 RPM using an overhead stirrerfitted with a 2-inch (5.1 cm) diameter stirring paddle. Sufficientisocyanate was then added to achieve the desired Isocyanate Index, andthe formulation was mixed well for about 6 seconds (s) at about 6,000RPM using the same stirrer. The 32-oz cup was dropped through a hole inthe bottom of a 128-oz (3804 ml) paper cup on a stand. The hole wassized appropriately to catch the lip of the 32-oz cup. The total volumeof the foam container was about 160 oz (4755 ml). Foams approximatedthis volume at the end of the foam forming reaction. Foam height overtime was recorded. String gel time and tack free time were measuredmanually with a wooden stick (e.g., tongue depressor or popsicle stick)and chronometer. Start time and rise time were determined with automatedrate of rise equipment.

In examples 1-7, various types and quantities of catalysts were used toproduce PIR/PUR foams of the present invention. Although the amounts ofeach catalyst are not the same in these examples, the respectivecatalyst quantities were chosen to provide similar string gel times.PIR/PUR foam properties are typically compared at equivalent string geltimes. In these examples, unless otherwise specified, the pphp valueslisted for the carboxylate salt catalysts exclude the additional weightof the diluent. Table I lists the components of the foam formulation andtheir respective pphp that are used in these examples.

TABLE I Formulations of Foams in Examples 1-7 (catalyst varied)COMPONENT PARTS (weight) Polyester Polyol 100 TCPP 4.7 Surfactant 1.7Polycat ® 5 catalyst 0.15 n-Pentane 17 Trimer Catalyst Varied IsocyanateIndex Varied (250-500)

Inventive Example 1

Comparison of a Potassium Pivalate Catalyst with Standard Catalysts

Sterically hindered carboxylate salt catalyst 1 was prepared bydissolving potassium hydroxide in ethylene glycol, followed byneutralization by the addition of an equivalent amount of pivalic acid.After neutralization, the water was removed by vacuum distillation. Theresulting approximate 50% solution of potassium pivalate (about 2 pphpor about 2 grams excluding diluent) in ethylene glycol constitutedinventive catalyst 1. Foams were made using the standard formulation inTable I at an Isocyanate Index of about 500.

Catalyst 1 was compared with two commercial standards, the DABCO® K15catalyst (70% potassium octoate solution) and the DABCO TMR® catalyst(75% 2-hydroxypropyltrimethylammonium octoate solution). Approximately4.6 pphp of the DABCO® K15 catalyst were used; excluding diluent, thisconverts to about 3.2 pphp or about 3.2 grams of potassium octoate.Approximately 4.8 pphp of the DABCO TMR® catalyst were used; excludingdiluent, this converts to about 3.6 pphp or about 3.6 grams of2-hydroxypropyltrimethylammonium octoate. Table II shows foam parameterssuch as start time, string gel time, height of string gel time (HSG),rise time and tack free time, for inventive catalyst 1 and the standardcatalysts. The string gel time for catalyst 1 was about 8 seconds longerthan for the standard catalysts. If more pphp of catalyst 1 were used todrop the string gel time to match the standard catalysts, the tack freetime would likewise drop. Hence, the tack free times for catalyst 1, theDABCO TMR® catalyst, and the DABCO® K15 catalyst are substantially thesame, suggesting similar surface curing time.

FIG. 1 compares the foam height versus time for inventive catalyst 1,the DABCO® K15 catalyst, and the DABCO TMR® catalyst. The DABCO® K15catalyst and catalyst 1 are both alkali metal carboxylate saltcatalysts; however, catalyst 1 is a sterically hindered alkali metalcarboxylate salt catalyst. The normalized foam height for catalyst 1 hasa more uniform slope and less pronounced plateau as compared to the thatof the DABCO® K15 catalyst. This translates to a more consistent foamheight rise and is a processing improvement relative to the DABCO® K15catalyst. Catalyst 1 does not have the smooth profile of foam heightversus time that is characteristic of the DABCO TMR® catalyst(2-hydroxylpropyltrimethylammonium octoate), but it is an improvementover the DABCO® K15 catalyst.

FIG. 2 illustrates that catalyst 1 has a smaller trimerization “step” ascompared to that of potassium octoate (the DABCO® K15 catalyst). TheDABCO® K15 catalyst has a long valley in between the two peaks,indicating the different foam rise speeds associated with foamproduction using this catalyst. Catalyst 1 represents an improvementover the DABCO® K15 catalyst in this regard. Neither the DABCO® K15catalyst nor catalyst 1 has a short valley between the peaks like theDABCO TMR® catalyst; this short valley is indicative of a lesssignificant trimerization step and a more consistent foam rise speedthroughout foam production.

The DABCO TMR® catalyst, however, can be thermally unstable at theelevated temperatures often encountered during PIR/PUR foam processing,decomposing into volatile amine by-products. Sterically hinderedcarboxylate salt catalyst 1 has thermal stability to over 150° C. andcan produce PIR/PUR foam which is substantially free of volatile aminesand amine odors.

Inventive Example 2

Comparison of a Dimethyldiallylammonium Pivalate Catalyst with StandardCatalysts

Sterically hindered carboxylate salt catalyst 2 was prepared by mixingan approximate 65% solution of dimethyldiallylammonium chloride in waterwith sodium hydroxide. The resulting dimethyldiallylammonium hydroxidewas dissolved in ethylene glycol, following by neutralization by theaddition of an equivalent amount of pivalic acid. After neutralization,the water was removed by vacuum distillation. The resulting approximate50% solution of dimethyldiallylammonium pivalate (about 2.5 pphp orabout 2.5 grams, excluding diluent) in ethylene glycol constitutedinventive catalyst 2. Foams were made using the standard formulation inTable I at an Isocyanate Index of about 500.

Catalyst 2 was compared with two commercial standards, the DABCO® K15catalyst (70% potassium octoate solution) and the DABCO TMR® catalyst(75% 2-hydroxypropyltrimethylammonium octoate solution). Approximately4.6 pphp of the DABCO® K15 catalyst were used; excluding diluent, thisconverts to about 3.2 pphp or about 3.2 grams of potassium octoate.Approximately 4.8 pphp of the DABCO TMR® catalyst were used; excludingdiluent, this converts to about 3.6 pphp or about 3.6 grams of2-hydroxypropyltrimethylammonium octoate.

As shown in Table II, at a slightly higher string gel time, inventivecatalyst 2 provided a tack free time of about 61 seconds, substantiallyequivalent to the tack free times of both the DABCO® K15 catalyst andthe DABCO TMR® catalyst. Inventive catalyst 2 thus produced a foamproduct with similar or slightly better surface cure rates and surfaceadherence during the manufacture of finished products such as laminatedfoam panels.

FIG. 3 compares the foam height versus time for inventive catalyst 2,the DABCO® K15 catalyst, and the DABCO TMR® catalyst. The catalyst 2curve has a slope that is more uniform than that of the DABCO® K15catalyst, and slightly less than that of the DABCO TMR® catalyst. Hence,foam produced with inventive catalyst 2 would have a more consistentfoam rise or foam expansion speed over time as compared to the DABCO®K15 catalyst. This is a desirable feature for continuous foamoperations, such as those operations which include lamination processes.The performance of catalyst 2 approaches the consistent foam height riseand processability associated with the DABCO TMR® catalyst, but catalyst2 does not have the thermal instability and amine order concerns of theDABCO TMR® catalyst.

Inventive Examples 3 and 4

Comparison of a Potassium Neodecanoate Catalyst and a PotassiumNeoheptanoate Catalyst with Standard Catalysts

Sterically hindered carboxylate salt catalyst 3 was prepared bydissolving potassium hydroxide in ethylene glycol, followed byneutralization by the addition of an equivalent amount of neodecanoicacid. After neutralization, the water was removed by vacuumdistillation. The resulting approximate 71% solution of potassiumneodecanoate (about 3.5 pphp or about 3.5 grams, excluding diluent) inethylene glycol constituted inventive catalyst 3. Similarly, stericallyhindered carboxylate salt catalyst 4 was prepared by dissolvingpotassium hydroxide in ethylene glycol, followed by neutralization bythe addition of an equivalent amount of neoheptanoic acid. Afterneutralization, the water was removed by vacuum distillation. Theresulting approximate 71% solution of potassium neoheptanoate (about 2.8pphp or 2.8 grams, excluding diluent) in ethylene glycol constitutedinventive catalyst 4. Foams using both catalysts 3 and 4 were made usingthe standard formulation in Table I at an Isocyanate Index of about 500.

Catalysts 3 and 4 were compared with two commercial standards, theDABCO® K15 catalyst (70% potassium octoate solution) and the DABCO TMR®catalyst (75% 2-hydroxypropyltrimethylammonium octoate solution).Approximately 4.6 pphp of the DABCO® K15 catalyst were used; excludingdiluent, this converts to about 3.2 pphp about or 3.2 grams of potassiumoctoate. Approximately 4.8 pphp of the DABCO TMR® catalyst were used;excluding diluent, this converts to about 3.6 pphp or about 3.6 grams of2-hydroxypropyltrimethylammonium octoate.

Table II summarizes foam parameters such as start time, string gel time,height of string gel time (HSG), rise time and tack free time, forinventive catalysts 3 and 4 and the standard catalysts. The string geltime for catalyst 3 was about 11 seconds longer than for the standardcatalysts, but even if it were matched, the tack free time would not besimilar to the standard catalysts. Catalyst 3 can be used to producequality PIR/PUR foam, but it is not as catalytically active as thestandard catalysts at this specific Isocyanate Index and foamformulation. The string gel time for catalyst 4 was about 6 secondslonger than for the standard catalysts. If more pphp of catalyst 4 wereused to decrease the string gel time to match the standard catalysts,the tack free time would likewise decrease. Hence, the tack free timesfor catalyst 4, the DABCO TMR® catalyst, and the DABCO® K15 catalyst aresubstantially the same, suggesting similar surface curing time.

Not wishing to be bound by theory, it is believed that the tack freetime and surface cure performance of catalyst 4 relative to catalyst 3can be explained by the length of the carbon chain attached to thecarboxylic moiety. Catalyst 3 (potassium neodecanoate) has 10 totalcarbon atoms, while catalyst 4 (potassium neoheptanoate) has 7 totalcarbon atoms. Not intending to be bound by this theory, but under theseparticular PIR/PUR foam conditions, the effect of the steric hindranceon catalyst activity appears to be impacted by the length of the carbonchain.

FIG. 4 compares the foam height versus time for inventive catalysts 3and 4, the DABCO® K15 catalyst, and the DABCO TMR® catalyst. The DABCO®K15 catalyst and catalysts 3 and 4 are alkali metal carboxylate saltcatalysts; however, catalysts 3 and 4 are sterically hindered alkalimetal carboxylate salt catalysts of different chain lengths. Thenormalized foam height curve for catalyst 3 has a more pronouncedplateau as compared to that of the DABCO® K15 catalyst. As with the tackfree time and surface cure data, catalyst 3 is not as catalyticallyactive as the standard catalysts at this particular foam formulation.However, catalyst 4 has a curve shape and slope very similar to that ofthe DABCO® K15 catalyst. Thus, catalyst 4 would be expected to providesimilar foam rise and processing characteristics relative to the DABCO®K15 catalyst. None of the catalysts in FIG. 4 have the smooth profile offoam height versus time that is characteristic of the DABCO TMR®catalyst (2-hydroxylpropyltrimethylammonium octoate). Stericallyhindered carboxylate salt catalysts 3 and 4, however, have thermalstability advantages over the DABCO TMR® catalyst. Catalysts 3 and 4 arethermally stable to over 150° C. and can produce PIR/PUR foams which aresubstantially free of volatile amines and amine odors.

TABLE II Foam comparison of catalysts 1-4 to standard catalysts StartString Rise Tack Time Gel Time HSG Time Free Time Catalyst [s] [s] [%][s] [s] ^(a)4.6 pphp DABCO ® K15 13 44 90 61 61 ^(b)4.8 pphp DABCO TMR ®20 44 83 50 60 ^(c)2 pphp Catalyst 1 22 52 83 70 69 ^(c)2.5 pphpCatalyst 2 18 48 86 65 61 ^(c)3.5 pphp Catalyst 3 14 55 80 85 100^(c)2.8 pphp Catalyst 4 15 50 88 66 67 Notes: ^(a)4.6 pphp DABCO ® K15catalyst including diluent converts to about 3.2 pphp of potassiumoctoate salt catalyst excluding diluent. ^(b)4.8 pphp DABCO TMR ®catalyst including diluent converts to about 3.6 pphp of2-hydroxypropyltrimethylammonium octoate catalyst excluding diluent.^(c)Catalyst 1-4 pphp values exclude the diluent.

Inventive Example 5

Comparison of a Tetramethylammonium Pivalate Catalyst with StandardCatalysts

Sterically hindered carboxylate salt catalyst 5 was prepared by mixingan approximate 25% solution of tetramethylammonium hydroxide in methanolwith ethylene glycol, followed by neutralization by the addition of anequivalent amount of pivalic acid. After neutralization, the methanoland the water were removed by vacuum distillation. The resultingapproximate 50% solution of tetramethylammonium pivalate (about 1.25pphp or about 1.25 grams, excluding diluent) in ethylene glycolconstituted inventive catalyst 5. Foams were made using the standardformulation in Table I at an Isocyanate Index of about 270.

Catalyst 5 was compared with two commercial standard catalyst solutions,the DABCO® K15 catalyst (70% potassium octoate solution) and the DABCOTMR® catalyst (75% 2-hydroxypropyltrimethylammonium octoate solution).Approximately 2.1 pphp of the DABCO® K15 catalyst were used; excludingdiluent, this converts to about 1.5 pphp or about 1.5 grams of potassiumoctoate. Approximately 2.9 pphp of the DABCO TMR® catalyst were used;excluding diluent, this converts to about 2.2 pphp or about 2.2 grams of2-hydroxypropyltrimethylammonium octoate.

As shown in Table III, at a similar string gel time, inventive catalyst5 had a tack free time of about 67 seconds, much shorter than thatachieved with either the DABCO® K15 catalyst or the DABCO TMR® catalyst.As such, catalyst 5 would produce foam with a faster surface cure, lesssurface friability, and subsequently, better adhesion performance inlaminated foam structures, as compared to either the DABCO® K15 catalystor the DABCO TMR® catalyst.

FIG. 5 compares the foam height versus time for inventive catalyst 5,the DABCO® K15 catalyst, and the DABCO TMR® catalyst. The curve forcatalyst 5 has a slope that is more uniform than either that of theDABCO® K15 catalyst or the DABCO TMR® catalyst. Hence, foam producedwith inventive catalyst 5 would have the most consistent foam rise orfoam expansion speed over time. This is a useful feature for continuousPIR/PUR foam operations, such as those involving lamination processes.

The near absence of a trimerization “step” with inventive catalyst 5 isillustrated further by both the short and the shallow valley between thetwo peaks in FIG. 6. Catalyst 5 offers a substantially consistent foamrise speed over a long time interval. This feature is highly desired inPIR/PUR foam production operations.

TABLE III Foam comparison of catalyst 5 to standard catalysts StartString Rise Tack Time Gel Time HSG Time Free Time Catalyst [s] [s] [%][s] [s] ^(a)2.1 pphp DABCO ® K15 14 54 91 72 108 ^(b)2.9 pphp DABCOTMR ® 16 49 91 65 77 ^(c)1.25 pphp Catalyst 5 20 50 83 70 67 Notes:^(a)2.1 pphp DABCO ® K15 catalyst including diluent converts to about1.5 pphp of potassium octoate salt catalyst excluding diluent. ^(b)2.9pphp DABCO TMR ® catalyst including diluent converts to about 2.2 pphpof 2-hydroxypropyltrimethylammonium octoate catalyst excluding diluent.^(c)Catalyst 5 pphp value excludes the diluent.

Inventive Example 6

Comparison of Inventive Catalyst Compositions Comprising a StericallyHindered Carboxylate Salt and an Optional Alkali Metal Carboxylate Salt(Potassium Octoate) with the Standard DABCO® K15 Potassium OctoateCatalyst

Inventive catalysts compositions were prepared by mixing a potassiumpivalate solution (a sterically hindered carboxylate salt; catalyst 1)with an alkali metal carboxylate salt solution in varying weight ratios.The alkali metal carboxylate salt was potassium octoate, commerciallyavailable in solution as the DABCO® K15 catalyst. Foams were made usingthe standard formulation in Table I at an Isocyanate Index of about 250and a catalyst loading of about 4.5% by weight of the total premix. Thepremix includes the components of the foam formulation in Table I otherthan the isocyanate.

A K15/Catalyst 1 weight ratio of about 3:1 including diluent converts toabout 4.2:1 excluding diluent. Similarly, a K15/Catalyst 1 weight ratioof about 1:1 including diluent converts to about 1.4:1 excludingdiluent.

FIG. 7 compares the foam height versus time for two different weightratios, including the diluent, of the DABCO® K15 catalyst to catalyst 1,and that of catalyst 1 used at 100% and the DABCO® K15 catalyst used at100%. As the amount of catalyst 1 (potassium pivalate) increasedrelative to the amount of the DABCO® K15 catalyst (potassium octoate), asmoother profile of foam height versus time resulted. Specifically, asthe amount of catalyst 1 increased, the foam height versus time curveshad more uniform slopes and less pronounced plateaus. The curve forcatalyst 1 (100% potassium pivalate) in FIG. 7 has the most consistentfoam rise over time, which is desirable for continuous PIR/PUR foamoperations.

FIG. 8 illustrates that the addition of catalyst 1 (potassium pivalate)to the DABCO® K15 catalyst reduces the depth and length of the valleybetween the peaks, indicating more consistent foam rise speeds. Catalyst1, as compared to the DABCO® K15 catalyst, has essentially one peak. Thepeak normally associated with the trimerization “step” has merged withthe larger peak. This desired kinetic profile is commonly observed inPUR foam, but is generally not found in PIR/PUR foam.

Inventive Example 7

Comparison of the Surface Friability of PIR/PUR Foams Produced UsingInventive Sterically Hindered Carboxylate Salts with Foam Produced froma Standard Mixed Carboxylate Salt Formulation.

Comparative catalyst 6 was prepared by mixing about 4.8 pphp of theDABCO® K15 catalyst (70% potassium octoate solution) with about 1.0 pphpof the Polycat® 46 catalyst (30% potassium acetate solution). Excludingdiluent, catalyst 6 includes about 3.4 pphp potassium octoate and about0.3 pphp of potassium acetate. Comparative catalyst 6 is a standardcatalyst formulation used in the commercial production of PIR/PUR foam.Inventive catalyst 7 comprised about 5.8 pphp of a 50%tetramethylammonium pivalate solution (excluding diluent, about 2.9pphp). The tetramethylammonium pivalate solution was produced asdescribed previously in Inventive Example 5. Inventive catalyst 8comprised about 5.8 pphp of a 50% potassium pivalate solution (excludingdiluent, about 2.9 pphp). The potassium pivalate solution was producedas described previously in Inventive Example 1. Foams were made usingthe standard formulation in Table I at an Isocyanate Index of about 250.

The resulting foams made with each catalyst were tested for surfacefriability in accordance with ASTM C421, which is summarized generallyas follows. The surface friability method determines the mass loss of apreformed block-type foam as a result of a combination of abrasion andimpact made by a laboratory tumbling mechanism. The test temperature iscontrolled at about 73° F. and humidity at about 50% relative humidity.Twelve (12) cubes of about ¾″ width of the foam material are weighedinitially and then placed in an oak box of specific dimensions, which isthen filled with twenty-four (24) oak cubes of about ¾″ width. The lidto the box is secured, and the box is rotated at about 60 revolutionsper minutes for a set number of revolutions (e.g., 600 totalrevolutions, 1200 total revolutions, etc.). At the conclusion of thetest, the foam contents are emptied onto an approximate ⅜″ mesh screenwhere the cubes are tapped gently to remove any dust or small particles.The twelve (12) cubes of foam are then weighed again. The mass loss isdefined by taking the difference of the original mass and the finalmass, dividing that difference by the original mass, and multiplying by100 to arrive at a percentage of mass loss.

The mass loss under ASTM C421 correlates with the surface friability ofthe foam. When the mass loss is high, the polymerized and crosslinkedfoam network at the surface of the foam is weak. That is, the surface isvery friable. Small foam particles at the surface break away easily,leading to poor or weak adhesion in laminated structures. Conversely,when the mass loss is low, the foam surface is less friable. These foamshave a strong surface network (crosslinked) and would be well suited forapplications such as laminations, where strong adherence to anothersubstrate can be required.

Table IV is a comparison of the surface friability of foams producedusing sterically hindered carboxylate salt catalysts (inventivecatalysts 7 and 8) with a foam produced using a standard industrycatalyst formulation (comparative catalyst 6). Percent mass loss isshown at about 600 and about 1200 revolutions (rev). The foam made fromcomparative catalyst 6 had poor friability performance. This foam hadsignificant mass loss, over 28% at 1200 revolutions, indicating a weakand friable foam surface. Foams made from sterically hinderedcarboxylate salt catalyst 7 and 8 had significantly less mass loss, andthus, have a much stronger and less friable surface. Consequently, wherestrong surface adherence is needed, performance can be improved inlaminated foams using sterically hindered carboxylate salt catalysts.

TABLE IV Surface friability comparison of foams produced using catalysts6-8 Friability Data % Mass Loss Catalyst 600 Rev 1200 Rev 6 15.9 28.5 74.7 11.3 8 2.2 9.4

Inventive Example 8

Comparison of a Hydrocarbon Blowing Agent with a TrichlorofluoromethaneBlowing Agent

Table V lists the composition of a comparative foam formulation 9, whichcan be used to produce PIR/PUR foams. Table VI lists the composition ofan inventive foam formulation 10. Compositions in these tables arelisted in weight percentages. The trimer catalyst used is inventivecatalyst 1, potassium pivalate, which was produced as describedpreviously in Inventive Example 1.

Comparative foam formulation 9 used trichlorofluoromethane as theblowing agent. Trichlorofluoromethane is a chlorofluorocarbon (CFC).Foams were produced using the foam formulation 9 in Table V with thetrichlorofluoromethane blowing agent; the Isocyanate Index wasapproximately 340. The inventive foam formulation 10 in Table VI wasselected to provide substantially equivalent foam height and foam volumeto that of the foam formulation 9, but with a hydrocarbon blowing agent,n-pentane. For comparison at substantially equivalent foam height andfoam volume, the foams produced using the foam formulation 10 utilized aslightly lower Isocyanate Index of about 280.

FIG. 9 compares the foam height versus time for comparative foamformulation 9—with the trichlorofluoromethane blowing agent—andinventive foam formulation 10, which used n-pentane as the blowingagent. As illustrated in FIG. 9, the trichlorofluoromethane blowingagent results in a much more rapid rise in the foam height as comparedto the n-pentane.

The presence of two distinct peaks in FIG. 10 illustrates that the rateof rise speed of foam produced using the trichlorofluoromethane blowingagent is not constant. Foam is expanding at drastically different ratesover time. This is particularly disadvantageous for continuous foamproduction lines, where the speed of the line cannot be adjusted tocompensate for the drastic changes in the rate of the foam rise. Incontrast, the foam produced using the n-pentane blowing agent provided asubstantially uniform foam rise speed over a significant time period.This is illustrated in FIG. 10 with the substantially horizontal line atthe constant foam rise rate of about 10 mm/sec over the time intervalfrom about 25 to about 45 seconds. This combination of inventivecatalyst 1 (a sterically hindered carboxylate salt, potassium pivalate)and a hydrocarbon blowing agent (n-pentane) provides a substantiallyconsistent foam rise speed over a long time interval, a highly desirablefeature for commercial PIR/PUR foam manufacturing operations.

Foam formulation 10 using the n-pentane blowing agent also includedwater and the Polycat® 5 catalyst (Table VI). A subsequent foaming testwas performed to determine if these materials may have impacted theresults illustrated in FIG. 9 or 10. When water and the Polycat® 5catalyst were removed, there was no significant change in the shape ofthe curves in FIGS. 9 and 10. The curves with the n-pentane blowing weremerely shifted to the right slightly (i.e., an increase in the starttime).

TABLE V Composition of Comparative Foam Formulation 9 COMPONENT WeightPercent (%) Polyester Polyol 24 TCPP 6.3 Surfactant 1.0Trichlorofluoromethane 12.6 Catalyst 1 1.3 MDI 54

TABLE VI Composition of Inventive Foam Formulation 10 COMPONENT WeightPercent (%) Polyester Polyol 30.1 TCPP 5 Surfactant 0.6 Polycat ® 5catalyst 0.05 n-Pentane 12.6 Water 0.15 Catalyst 1 0.9 MDI 55.2

The invention claimed is:
 1. A composition comprising: i) at least onepolyol, wherein the polyol includes a reaction product of at least oneof ethylene oxide or propylene oxide with at least one of ethyleneglycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexanediol, sucrose, ethylenediamine, diethylenetriamine, or a reactionproduct of at least one of adipic acid, phthalic acid, or phthalicanhydride with at least one of ethylene glycol, propylene glycol,1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol,diethylene glycol, dipropylene glycol, pentaerythritol, glycerol,diglycerol, trimethylol propane, or butanediol; ii) about 10 to about 80parts by weight per hundred weight parts of polyol of at least onehydrocarbon blowing agent, wherein the at least one hydrocarbon blowingagent comprising at least one member selected from the group consistingof n-pentane, iso-pentane and cyclopentane, with the proviso that the atleast one blowing agent is not a chlorofluorocarbon; iii) about 0.5 toabout 10 pphp of at least one silicon surfactant; iv) greater than zeroto about 10 pphp water; v) greater than zero to about 50 pphp flameretardant; vi) greater than zero to about 10 pphp of at least oneurethane catalyst, wherein the urethane catalyst includespentamethyldiethylenetriamine or pentamethyldipropylenetriamine; andvii) about 0.05 to about 10 pphp of a catalyst composition comprising atleast one sterically hindered carboxylate salt selected from the groupconsisting of potassium triethylacetate, potassium pivalate, potassiumneoheptanoate, potassium neodecanoate, tetramethyl ammonium pivalate,dimethyldiallylammonium pivalate, tetramethylammonium neoheptanoate,tetramethylammonium neodecanoate, and combinations thereof.
 2. Acomposition comprising the contact product of: (a) at least one activehydrogen-containing compound selected from the group consisting of atleast one polyether polyol, at least one polyester polyol, andcombinations thereof; (b) a catalyst composition comprising at least onesterically hindered carboxylate salt selected from the group consistingof potassium pivalate, tetramethylammonium pivalate,2-hydroxyl-propyltrimethylammonium pivalate,2-hydroxylpropyltriethylammonium pivalate, tetraethylammonium pivalate;and (c) at least one blowing agent comprising at least one memberselected from the group consisting of water, n-pentane, iso-pentane andcyclopentane, with the proviso that the at least one blowing agent isnot a chlorofluorocarbon; (d) at least one polyisocyanate selected fromthe group consisting of 2,4-toluene diisocyanate or 2,6-toluenediisocyanate; and wherein the isocyanate index is between 150 to
 270. 3.The composition of claim 2, wherein the at least one sterically hinderedcarboxylate salt includes tetramethylammonium pivalate.
 4. Thecomposition of claim 2, wherein the at least one activehydrogen-containing compound includes a reaction product of at least oneof ethylene oxide or propyleneoxide, with at least one of ethyleneglycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexanediol, sucrose, ethylenediamine, diethylenetriamine, tolylenediamine,diphenylmethanediamine, or triethanolamine.
 5. The composition of claim2, wherein the at least one active hydrogen-containing compound includesa reaction product of at least one of adipic acid, phthalic acid, orphthalic anhydride, with at least one of ethylene glycol, propyleneglycol, 1,3-butanediol, 1,4-butane diol, 1,6-hexane diol, neopentylglycol, diethylene glycol, dipropylene glycol, pentaerythritol,glycerol, diglycerol, trimethylol propane, or butanediol.
 6. Thecomposition of claim 2, further comprising at least one siliconsurfactant and at least one flame retardant.
 7. The composition of claim6, wherein the at least one blowing agent is present in about 10 toabout 80 parts by weight per hundred parts (pphp) of polyol; and whereinthe catalyst composition is present in an amount between about 0.05 toabout 10 pphp; and wherein the at least one silicon surfactant ispresent in an amount between about 0.5 to about 10 pphp; and wherein theat least one flame retardant is present in an amount greater than zeroto about 50 pphp.
 8. The composition of claim 7, wherein the at leastone blowing agent includes water and at least one of n-pentane,iso-pentane, or cyclopentane; and wherein the water is present in anamount greater than zero and less than about 10 pphp.
 9. The compositionof claim 8, wherein the at least one blowing agent is present in about16 to about 40 parts by weight per hundred weight parts (pphp) ofpolyol; and wherein the catalyst composition is present in an amountbetween about 0.8 to about 8 pphp; and wherein the at least one siliconsurfactant is present in an amount between about 0.7 to about 4 pphp;and wherein the at least one flame retardant is present in an amountgreater than zero to about 7 pphp; and wherein the water is present inan amount greater than zero and less than about 4 pphp.
 10. Thecomposition of claim 2, wherein the at least one activehydrogen-containing compound includes a reaction product of at least oneof ethylene oxide or propyleneoxide with at least one of ethyleneglycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol,pentaerythritol, glycerol, diglycerol, trimethylol propane, cyclohexanediol, sucrose, ethylenediamine, diethylenetriamine, tolylenediamine,diphenylmethanediamine, or triethanolamine.
 11. The composition of claim2, wherein the at least one active hydrogen-containing compound includesa reaction product of at least one of adipic acid, phthalic acid, orphthalic anhydride with at least one of ethylene glycol, propyleneglycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentylglycol, diethylene glycol, dipropylene glycol, pentaerythritol,glycerol, diglycerol, trimethylol propane, or butanediol.
 12. Thecomposition of claim 2, further comprising a urethane catalyst selectedfrom the group consisting of 1,2-dimethylimidazole, N-methylmorpholine,N-ethylmorpholine, triethylamine, N,N′-dimethylpiperazine,1,3,5-tris(dimethylaminopropyl)hexahydrotriazine,2,4,6-tris(dimethylaminomethyl)phenol, pentamethyldipropylene triamine,N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine,pentamethyldiethylenetriamine, hexamethyltriethylenetetramine,heptamethyltetraethylenepentamine, pentamethyldipropylenetriamine,dimethylethanolamine, bis(dimethylaminoethyl)ether,tris(3-dimethylamino)propylamine, 1,8-diazabicyclo[5.4.0]undecene, andcombinations thereof.
 13. The composition of claim 12, wherein theurethane catalyst includes pentamethyldiethylenetriamine orpentamethyldipropylenetriamine.
 14. The composition of claim 2, furthercomprising at least one alkali metal a,B-unsaturated carboxylate salt,at least one alkali metal carboxylate salt, at least one quaternaryammonium a,B-unsaturated carboxylate salt, or at least one quaternaryammonium carboxylate salt, or any combination thereof.
 15. Thecomposition of claim 2, further comprising at least one diluent.